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United States Patent 1,4 DI (POLYALKYLPIIENYLAMINO)ANTHRA- QUINONE CONTAINING A SULFATOACETA- MIDOMETHYL SUBSTITUENT Jacques Guenthard, Binningen, Basel-Land, Wolfgang Schoenauer, Riehen, and Francois Benguerel, Basel, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland No Drawing. Filed Jan. 22, 1962, Ser. No. 167,971 4 Claims. (Cl. 260-377) This invention relates to a process for the production of dyes which contain, combined to a carbon atom, at least one group of the formula wherein R represents a substituted or unsubstituted aliphatic, aliphatic-aromatic or aliphatic-cyclo aliphatic radical which may contain hetero atoms.

In this formula OR--CO may have, for example, one of the following meanings:

but it is preferably OCH CO-.

The process for the production of the dyes is characterized by the reaction of dyes having exchangeable hydrogen atoms bound to aromatic nuclei, or organic compounds having exchangeable hydrogen atoms bound to aromatic nuclei and in addition at least one substituent permitting dye formation, with a compound of the formula wherein R represents a substituted or unsubstituted aliphatic, aliphatic-aromatic or aliphatic-cycloaliphatic radical which may contain hetero atoms, and

X represents OH or OSO H,

and a symmetrical dihalogenodimethyl ether.

The preferred dyes in which a compound of the Formula II or an equivalent mixture of a compound of the Formula III and a symmetrical dihalogenodimethyl ether occur at least once, are the dyes of the anthraquinone series, and of these the preferred dyes are the anthraquinone dyes in which the chain member R is the methylene group.

The following may be enumerated as examples of dyes possessing exchangeable hydrogen atoms: l-amino- 4-arylaminoanthraquinones such as 1-amino-4-phenylaminoanthraquinone-Z-sulfonic acid, and its derivatives substituted in the phenylamino radical by methyl, ethyl, methoxy, ethoxy, chlorine or bromine, such as l-amino- 4-(2,4'-dimethyl)-, -4-(2,6-dimethyl)-, 4-(2,4,6'-trimethyl)phenylaminoanthraquinone-Z-sulfonic acid, 1,4- diarylaminoanthraquinones and their sulfonic acids such as l,4-di-(4-methyl)- or 4-methyl-2'-sulfophenylaminoanthraquinone, 1,4-di-(2,4,6'-trimethyl)- or -(2',4,6'- trimethyl-3 '-sulfo phenylaminoanthraquinone, l-amino- 2-aryIoxy-4-arylamin'oanthraquinones such as l-amino-Z- (4-octyl)-phenoxy 4 (2,4,6" trimethyl) phenylaminoanthraquinone and its sulfonic acids, in which the anthraquinone nucleus may be further substituted.

The reaction is carried out in an acid medium, preferably in sulfuric acid solution, e.g. to sulfuric acid, at temperatures of 0 to about 60 C. for several hours.

The reaction products, when they contain no acid sulfate group, are either sulfated in the reaction medium itself by the addition of concentrated oleum until a 100% sulfuric acid or a weak oleum is formed, or they are first isolated, e.g. by being run into ice and water, filtered off, washed neutral with dilute brine and dried with vacuum, and then sulfated in 100% sulfuric acid or weak oleum. The sulfating mixture is discharged onto ice and water or into brine; on which the sulfuric acid ester is salted out, filtered with suction, washed neutral with brine and dried.

The compounds of Formula II can be obtained from the corresponding carboxylic acid amides of Formula III by condensation with aldehydes, preferably formaldehyde, or with a symmetrical dihalogenodimethyl ether in neutral to weakly alkaline aqueous solution or suspension at room temperature or a higher temperature and in presence of a catalyst, e.g. trimethylor triethylamine.

The dyes obtained dye wool, silk, synthetic polyamide fibers, leather and fibers of neutral and regenerated cellulose by exhaustion dyeing, padding and printing processes in shades which are fast to light and wet treatments, of good fastness to milling, water, sea water, washing, perspiration, crocking and of very good fastness to dry cleaning. The introduction of at least one group of Formula II or of an equivalent mixture of a compound of Formula III and a symmetrical dihalogenodimethyl ether improves the milling fastness in particular while leaving the light and other wet fastness properties unafi'ected.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 4.7 parts of the condensation product of 1 mol of 1,4- diaminoanthraquinone and 2 moles of 1-bromo-2,4,6-trimethylbenzene are dissolved in 74 parts of 96% sulfuric acid at 20, then 2.2 parts of N-methylol-hydroxyacetamide. are added with stirring at l-l5. The mixture is stirred for 24 hours at 1520 and then run onto ice. The precipitated dye is isolated, washed with a sodium chloride solution until neutral and dried. The dye is obtained as a blue powder which dyes wool in full blue shades of very good fastness to washing and to acid and alkaline milling.

The dyeings on wool are considerably faster to milling 4 mixture is stirred for 24 hours at -20" and then run into ice. The product is worked up as described in Example 1, the dye being obtained as a blue-violet powder. It dyes wool in full blue-violet shades of very good fastness to washing and to acid and alkaline milling.

DYEING EXAMPLE (EXAMPLE 1 6) A dyebath is prepared with 10,000 parts of water, 2 parts of the dye of Example 1, 10 parts of Glaubers salt and 2 parts of glacial acetic acid. 100 parts of wool 10 than dyeings produced with the sulfonation product of fabric are entered at 40-45 the bath brought t0 the boll 1, ,-di-(2',4',6'-trim thyl)-phenylaminoanthraquinone, in 30 minutes and maintained at the boil for a further 30 EXAMPLE 2 minutes. Another 2 parts of glacial acetic acid are added and dyeing completed in another 30 minutes at the boil. 5 parts of the condensation product of 1 mol of 1,4- 15 The wool is removed, rinsed and dried. It is dyed in a diaminoanthraquinone and2 mols of 1-bromo-2,4-dimeth full, level blue shade of very good washing and acid yl-6-ethylbenzene are dissolved in 74 parts of 96% suland alkaline milling fastness while the fastness to light, furic acid at 15-20". 2.2 parts of N-methylolhydroxywater, sea water, perspiration and crocking is excellent. acetamide are added with stirring. The product is In the following Table A further dyes are set forth worked up as described in Example 1. The dye obtained which are obtainable according to the particulars given gives bright, level blue shades of good depth on wool; in Examples 1 to 5. They correspond to the formula the fastness to light, washing, acid and alkaline milling is excellent, better than the fastness shown by dyeings of 0 NH 4, the sulfonation product of 1,4-di-(2,4-dimethyl-6-ethyl)- H phenylarninoanthraquinone. 6 5' X EXAMPLE 3 5.3 parts of the condensation product of 1 mol of 1,4- diarninoanthraquinone and 2 mols of 1-bromo-2,4-dieth- A 1 ylbenzene are dissolved in 74 parts of 96% sulfuric acid at 15-20. 2.2 parts of N-methylolhydroxyacetamide X are added With Vigorous stiffing- The Product is Worked wherein the figures indicate the positions of the various up as described in Example 1 to give a dye for W001. The snbstituents and X represents the grouping dyeings are of green shade, bright, level and of good depth, with very good light fastness, excellent acid and CH2 NH OCCI:I2O SO3H alkaline milling fastness, and good perspiration and washand is present at least once 1n each molecule of the ing fastness. dye.

Table A Example Shade of N0. 2' a 4' 5' 6 2' 3' 4" 5 e dyeing on X CgHs H CzH5 CH3 X C1115 H C2115 Blue. X CzHs H C2H5 C2H5 X CzHs H CzH5 D0. X H CH3 H CH3 X H CH3 H Green. X 0H3 H H CH3 X OH; H H D0 X H CH3 CH3 X H H CH3 Blue. H CzHs X CH3 B! H C2H5 X CH3 Blue-red CH3 X CH3 CH3 CH3 CH X CH3 CH3 Blue. X CH3 H CzH5 CH3 X CH3 H C2115 D0. X C3H1 H 0,115 CH3 X 03H? H 02115 D0. X C2115 H C2115 CH3 H CzHr; H C2H5 D0. X CzH5 H CgHs C2115 H CzHs H C2115 D0. X CH3 H CzHs CH3 H CH3 H CgHs D0. X I'I 1'1 CzH5 C2H5 H H H CZH5 D0. X H OH; H OH; H H CH3 Green. X OH; H H CH3 H OH; H H De. X H H CH3 CH3 H H H CH3 Blue. H C2H5 X CH3 Br H C2H5 H CH3 Blue-red CH3 X CH3 CH3 CH3 CH3 H CH3 CH3 B1116. X CaH- H C2115 CH3 H C3H7 H CzHs 0 X 04m H Br CH X oiHg H Br Blue-red X C4119 H Br OH: H C4He H Br 0 X C4119 H CH3 CH3 X C4Hg H CH3 Blue X C4Hg H CH3 CH3 H CAHQ H CH3 0 EXAMPLE 4 r In the following Table -B are set forth further dyes which can be obtained according to the particulars given in 4.7 parts of the condensation product of 1 mol of 1,4- Exam le 1 to 5. They correspond to the formula, diarninoanthraquinone and 2 mols of 1-brorno-2,4,6-tri- O methylbenzene are dissolved in 74 part of 96% sulfuric H A acid at 20. 1.4 parts of N-methylolhydroxyacetamide 7 8 1 2 are added at 10-15 with vigorous stirring. The mixture is stirred for 24 hours at 1520 and then run into ice. 6 5 4 3 I I It is worked up into a dye in the way described in Ex- I 2 3 X ample 1. o NH-O4J EXAMPLE 5 7 0 3.5 parts of 1-amino-4-(2',4',6'-trimethyl)-phenylaminoanthraquinone are dissolved in 74 parts of 96% sulfuric acid at 20. 1.1 parts of N-methylol hydroxyacetamide are added at 10-15 with vigorous stirring. The

wherein/the figures indicate the positions of the different substituen'ts and X represents the grouping 75 (Formula 1, supra).

7 8 EXAMPLE 43 2. The anthraquinone dye of the formula CH3 CH3 JHrNH-c o-cm-o-soarl 1 OHB-NH-CO-CHT-O-SOQH NH CH3 7 NH- CH3 N 5 01- H 3 C1 CH3 I (I311; Cl HzNH-OOCHa-OSOaH CH -NH-CO-GHz-O-SOaH 2 0 141100111 (EH3 (3H8 3. The anthraquin'one dye of the formula (3H3 (|JH NHO O-GHr-O-SOaH 1 EXAMPLE 44 1H3 CH3 (i'lHa (EHrNH-GO-CHr-O-SOsH HO (f NH- IHa JzHs CH 4. The anthraquinone dye of the formula I l a CH -NH-O O-'CHz--O-'SOaH Y (2H1 $HPNH-C OCHgO-SO3H H 0 NH- CH3 0 NH-O-cm I I CH CHg-NHC O-GHrO-SOaH 6 NH CH3 Havrng thus d1sclosed the mventwn what we clarm 1s: 1. An anthraquinone dye of the formula R References Cited by the Examiner cm-NH-c wn-04,0313 UNITED STATES PATENTS 0 NH R; 2,226,909 12/40 Peter 260-381 XR l 2,236,672 4/41 Cofley et a1 260-381 XR R1 2,245,780 6/41 Heinrich 1 260-377 XR 2,335,680 111/43 Klein 260-377 1.11 2,419,405 4/47 Klein 260-377 XR H 2,427,527 9/47 Gutzwiller 260-374 0 NE-Q-m 2,677,694 5/54 Randall et a1 260-377 XR l H, 0 v 2,975,167 3/61 Schwander 260199 FOREIGN PATENTS 1,181,107 1/59 France. 1,217,738 12/59 France. w he ein t b 1 df th OTHER REFERENCES 1 represen s a men er se ecte 1 rom e group consisting of methyl and y logegmanml. .Textrl Praxrs, October 1958, pp. 1056- R represents a member selected from the group consist methyl and ethyl/and LORRAINE A. WEINBERGER e E R represents a member selected from the group c onsist- Pnmmy Exammer" ing of hydrogen, methyl and ethyl, LEON ZITV'ER? Examine?" 

4. THE ANTHRAQUINONE DYE OF THE FORMULA 